CN100503540C - Method for preparing alkyl orthoacetate - Google Patents
Method for preparing alkyl orthoacetate Download PDFInfo
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- CN100503540C CN100503540C CNB2007101133388A CN200710113338A CN100503540C CN 100503540 C CN100503540 C CN 100503540C CN B2007101133388 A CNB2007101133388 A CN B2007101133388A CN 200710113338 A CN200710113338 A CN 200710113338A CN 100503540 C CN100503540 C CN 100503540C
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Abstract
The invention relates to a preparation method of alkyl ester orthoacetate. According to the molar ratio of acetonitrile, anhydrous aliphatic alcohol and acetyl chloride, which is 1.0:1.5-3.5:0.8-1.3, acetyl chloride is dripped in the mixture of acetonitrile and aliphatic alcohol at a temperature between -10 DEG C and 0 DEG C, after the dripping, salt-forming reaction lasts for four to forty eight hours at a temperature between -20 DEG C and 45 DEG C, the pH value of reaction liquid does not need to be adjusted, the anhydrous aliphatic alcohol with a molar ratio value two to five times larger than the molar ratio value of the acetonitrile is then added into the reaction liquid, and the reaction liquid undergoes alcoholysis reaction for four to twenty four hours at a temperature between -20 DEG C and 67 DEG C, so that the alkyl ester orthoacetate is produced. In the process of reaction, the invention does not need to use other solvent and regulate the pH value of the reaction. The invention has the advantages of simple operation of the reaction technique, low cost, little environmental pollution and high yield.
Description
Technical field
The invention belongs to the organic synthesis field, particularly a kind of acetonitrile, Fatty Alcohol(C12-C14 and C12-C18) and Acetyl Chloride 98Min. of utilizing do not need to add other materials and makees solvent, do not need the pH of conditioned reaction liquid to prepare the method for alkyl ortho-acetate.
Background technology
Alkyl ortho-acetate, particularly trimethyl orthoacetate and triethly orthoacetate are the intermediates of important pyrethroid Permanone and Cypermethrin, also can be used as synthesis material, sensitive materials additive and the special solvent of dyestuff.According to the literature, trimethyl orthoacetate or triethyl mainly contain following 4 kinds of route of synthesis:
1.Geuther1871 year (document Zeitschift f ü r chimie1871,128) propose, trichloroethane and sodium alkoxide prepared in reaction alkyl ortho-acetate, Wang Jiajun, Hu Xiuxiang (document " triethly orthoacetate is synthesized in phase transfer method catalysis ", " Tianjin chemical industry " 11 monthly magazines in 2003, the 17th the 6th phase of volume) use trichloroethane and ethanol, sodium hydroxide to prepare alkyl ortho-acetate by phase transfer reaction, the yield valency is low.
2.Frederick and S.M.McElvain (document The Preparation and Properties of KeteneDiethylacetal[J] .Journal of the American Chemical Society, 1936,58:529～531) propose, methylene malonic acid dimethyl ester or diethyl ester and methyl alcohol or ethanol addition reaction, generate trimethyl orthoacetate or triethyl, cost is too high, is not suitable for suitability for industrialized production.
3.McBaneM.S (document Thesis1941) proposes, grignard reagent methyl-magnesium-bromide and orthocarbonic ester generate trimethyl orthoacetate or triethyl, and production cost is higher, only suitable research experiment.
4.PeterPT.Sah. (document Esters of Ortho-Acetic Acid[J] .Journal of the
American Chemical Society, 1928,50:516～518) and patent JP55087734, JP55040611, JP52125108, JP5108012 and ES8404673 etc. use acetonitrile, methyl alcohol or ethanol, hydrogenchloride, ethyliminum base ether hydrochloride is produced in reaction earlier in suitable solvent, adjust pH then, add alkyl alcohol, alcoholysis generates trimethyl orthoacetate or triethyl, industrial both at home and abroad now all at this route of use, there is following shortcoming in this route:
1) uses a large amount of solvents;
2) industrial, the feeding of hydrogen chloride gas is measured inaccurate;
3) to use the pH of alkaline matter conditioned reaction before second step, reaction was carried out.
Summary of the invention
Technical problem to be solved by this invention provides a kind of new method for preparing alkyl ortho-acetate, and this method is fairly simple, yield is higher, and cost is lower.
The present invention prepares the method for alkyl ortho-acetate, it is characterized in that according to acetonitrile, anhydrous fatty alcohol, Acetyl Chloride 98Min. mol ratio be the ratio of 1.0:1.5～3.5:0.8～1.3,-10～0 ℃ of dripping acetyl chloride in the mixture of acetonitrile, anhydrous fatty alcohol, after dripping end,-20～45 ℃ of salt-forming reactions 4～48 hours, in reaction solution, add anhydrous fatty alcohol then again, add-on is 2.0～5.0 times of acetonitrile mole number,-20～65 ℃ of alcoholysis reactions 4～24 hours, obtain alkyl ortho-acetate.
Technological line of the present invention is as follows:
Alkyl acetate and anhydrous hydrogen chloride that the present invention uses Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) reaction to generate, the alkyl acetate of by-product is made solvent, anhydrous hydrogen chloride directly with acetonitrile, Fatty Alcohol(C12-C14 and C12-C18) salt-forming reaction generation inferior amine salt hydrochlorate, the inferior amine salt hydrochlorate carries out alcoholysis reaction with Fatty Alcohol(C12-C14 and C12-C18) again, generates alkyl ortho-acetate.After the first step salt-forming reaction finishes, do not need to use the pH of alkaline matter conditioned reaction liquid, directly add the Fatty Alcohol(C12-C14 and C12-C18) of second section alcoholysis reaction needs, carry out the second step alcoholysis reaction.
Wherein preferred technical qualification are:
The first step salt-forming reaction, the mol ratio of acetonitrile, anhydrous fatty alcohol, Acetyl Chloride 98Min. are 1.0:2.1:1.0.
The salt-forming reaction condition :-5～25 ℃ were reacted 6 hours.
The alcoholysis reaction condition: 25～45 ℃ were reacted 8 hours.
The second step alcoholysis reaction acetonitrile: Fatty Alcohol(C12-C14 and C12-C18)=1:2.0～5.0 (mol ratio), preferred 1:2, promptly the add-on of Fatty Alcohol(C12-C14 and C12-C18) is 2.0 times of acetonitrile mole number.
Fatty Alcohol(C12-C14 and C12-C18) of the present invention is CnH
2n+
1OH, n=1～6, particular methanol or ethanol.
Advantage of the present invention:
1, the reaction of Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) generates the required anhydrous hydrogen chloride of salify, need not additional equipment and prepares anhydrous hydrogen chloride, has reduced the step and the equipment of preparation anhydrous hydrogen chloride, has reduced investment.
2, the reaction of Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) generates the required anhydrous hydrogen chloride of salify, and the add-on by the control Acetyl Chloride 98Min. is controlled to the required anhydrous hydrogen chloride of reactant salt, and the growing amount that makes anhydrous hydrogen chloride accurately and reliably.
3, the reaction of Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) generates the required anhydrous hydrogen chloride of salify, after anhydrous hydrogen chloride generates immediately with acetonitrile, Fatty Alcohol(C12-C14 and C12-C18) salt-forming reaction, reaction solution acidity can be very not high, reduced to the corrosion of equipment with to the pollution of environment.
4, the reaction of Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) generates alkyl acetate, and alkyl acetate does not need to add other compounds as solvents as the required solvent of reaction.
5, alkyl acetate itself is exactly a by product for preparing alkyl ortho-acetate, and Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) reaction generate alkyl acetate and make solvent, do not increase other compounds in the reaction solution, have reduced the recovery of solvent, and the separation of product is more prone to.
6, quantitative Acetyl Chloride 98Min. and Fatty Alcohol(C12-C14 and C12-C18) reaction quantitatively generates the salt-forming reaction that anhydrous hydrogen chloride carries out, and no longer need use in the alkaline matter and excessive anhydrous hydrogen chloride before alcoholysis, has simplified technological operation.
Embodiment
The present invention is further elaborated below in conjunction with embodiment, but do not limit the present invention.
Embodiment 1:
Salt-forming reaction feed molar proportioning: acetonitrile: anhydrous methanol: Acetyl Chloride 98Min.=1:2.1:1.05
Operation: stirring, thermometer, condenser and dropping funnel are installed on the 500ml four-hole bottle, add acetonitrile 41g (pure) in the bottle, methyl alcohol 67.2g (pure) cools to below-10 ℃ under stirring, and beginning dripping acetyl chloride 82.5g (pure) temperature is controlled at-10～0 ℃.After adding Acetyl Chloride 98Min., reaction solution is slowly heated up 20 ℃ react and finished salt-forming reaction in 6 hours.
Add methyl alcohol 64g (pure) again in the four-hole reaction flask, be warmed up to 45 ℃ of alcoholysis 8 hours under stirring, alcoholysis reaction finishes, cool to 0 ℃ of filtration, remove by-product ammonium chloride, solid ammonium chloride uses the small amount of methanol washing, and filtrate adds rectifying in the rectifying bottle, at first reclaim the solvent acetic acid methyl esters of unreacted methanol and generation, collect trimethyl orthoacetate at last, 102g must be measured in bp.108 ± 1 ℃, gas chromatographic analysis content is greater than 98%, reaction yield 83%.
Embodiment 2:
Salt-forming reaction feed molar proportioning: acetonitrile: dehydrated alcohol: Acetyl Chloride 98Min.=1:2.1:1.05
Operation: stirring, thermometer, condenser and dropping funnel are installed on the 500ml four-hole bottle, add acetonitrile 41g (pure) in the bottle, dehydrated alcohol 96.6g (pure) cools to below-5 ℃ under stirring, and beginning dripping acetyl chloride 82.5g (pure) temperature is controlled at-5～0 ℃.After adding Acetyl Chloride 98Min., reaction solution is slowly heated up 35 ℃ react and finished salt-forming reaction in 8 hours.
Add ethanol 92g (pure) again in the four-hole reaction flask, be warmed up to 50 ℃ of alcoholysis 8 hours under stirring, alcoholysis reaction finishes, cool to 0 ℃ of filtration, remove by-product ammonium chloride, solid ammonium chloride uses the small amount of methanol washing, and filtrate adds rectifying in the rectifying bottle, at first reclaim the solvent ethyl acetate of unreacted ethanol and generation, collect triethly orthoacetate at last, 129g must be measured in bp.145～148 ℃, gas chromatographic analysis content is greater than 98%, reaction yield 78%.
Embodiment 3:
Salt-forming reaction feed molar proportioning: acetonitrile: anhydrous methanol: Acetyl Chloride 98Min.=1:2.5:1.15
Operation: stirring, thermometer, condenser and dropping funnel are installed on the 500ml four-hole bottle, add acetonitrile 41g (pure) in the bottle, methyl alcohol 67.2g (pure) cools to below-10 ℃ under stirring, and beginning dripping acetyl chloride 90.3g (pure) temperature is controlled at-10～0 ℃.After adding Acetyl Chloride 98Min., reaction solution is slowly heated up 25 ℃ react and finished salt-forming reaction in 4 hours.
Add methyl alcohol 64g (pure) again in the four-hole reaction flask, be warmed up to 45 ℃ of alcoholysis 6 hours under stirring, alcoholysis reaction finishes, cool to 0 ℃ of filtration, remove by-product ammonium chloride, solid ammonium chloride uses the small amount of methanol washing, and filtrate adds rectifying in the rectifying bottle, at first reclaim the solvent acetic acid methyl esters of unreacted methanol and generation, collect trimethyl orthoacetate at last, 95.5g must be measured in bp.108 ± 1 ℃, gas chromatographic analysis content is greater than 98%, reaction yield 78%.
Embodiment 4:
Salt-forming reaction feed molar proportioning: acetonitrile: dehydrated alcohol: Acetyl Chloride 98Min.=1:2.3:1.10
Operation: stirring, thermometer, condenser and dropping funnel are installed on the 500ml four-hole bottle, add acetonitrile 41g (pure) in the bottle, dehydrated alcohol 105.8g (pure) cools to below-5 ℃ under stirring, and beginning dripping acetyl chloride 86.4g (pure) temperature is controlled at-5～0 ℃.After adding Acetyl Chloride 98Min., reaction solution is slowly heated up 35 ℃ react and finished salt-forming reaction in 6 hours.
Add ethanol 92g (pure) again in the four-hole reaction flask, be warmed up to 45 ℃ of alcoholysis 6 hours under stirring, alcoholysis reaction finishes, cool to 0 ℃ of filtration, remove by-product ammonium chloride, solid ammonium chloride uses the small amount of methanol washing, and filtrate adds rectifying in the rectifying bottle, at first reclaim the solvent ethyl acetate of unreacted ethanol and generation, collect triethly orthoacetate at last, 124g must be measured in bp.145～148 ℃, gas chromatographic analysis content is greater than 98%, reaction yield 75%.
Embodiment 5:
Salt-forming reaction feed molar proportioning: acetonitrile: anhydrous methanol: Acetyl Chloride 98Min.=1:2.1:1.05
Operation: stirring, thermometer, condenser and dropping funnel are installed on the 500ml four-hole bottle, add acetonitrile 41g (pure) in the bottle, methyl alcohol 67.2g (pure) cools to below-5 ℃ under stirring, and beginning dripping acetyl chloride 82.5g (pure) temperature is controlled at-5～0 ℃.After adding Acetyl Chloride 98Min., reaction solution is slowly heated up 25 ℃ react and finished salt-forming reaction in 10 hours.
Add methyl alcohol 64g (pure) again in the four-hole reaction flask, be warmed up to 45 ℃ of alcoholysis 12 hours under stirring, alcoholysis reaction finishes, cool to 0 ℃ of filtration, add the ammoniacal liquor of 150ml5%, the dissolving by-product ammonium chloride, static layering, organic layer added the 10g Anhydrous potassium carbonate dry 4 hours, added after the filtration drying agent in the rectifying bottle, at first reclaim the solvent acetic acid methyl esters, collect trimethyl orthoacetate at last, 104g must be measured in bp.108 ± 1 ℃, gas chromatographic analysis content is greater than 98%, reaction yield 85%.
Embodiment 6:
Salt-forming reaction feed molar proportioning: acetonitrile: dehydrated alcohol: Acetyl Chloride 98Min.=1:2.1:1.10
Operation: stirring, thermometer, condenser and dropping funnel are installed on the 500ml four-hole bottle, add acetonitrile 41g (pure) in the bottle, methyl alcohol 67.2g (pure) cools to below-10 ℃ under stirring, and beginning dripping acetyl chloride 86.4g (pure) temperature is controlled at-10～0 ℃.After adding Acetyl Chloride 98Min., reaction solution is slowly heated up 35 ℃ react and finished salt-forming reaction in 12 hours.
Add ethanol 92g (pure) again in the four-hole reaction flask, be warmed up to 45 ℃ of alcoholysis 12 hours under stirring, alcoholysis reaction finishes, cool to 0 ℃ of filtration, add the ammoniacal liquor of 150ml5%, the dissolving by-product ammonium chloride, static layering, organic layer added the 10g Anhydrous potassium carbonate dry 8 hours, added after the filtration drying agent in the rectifying bottle, at first reclaim solvent ethyl acetate, collect triethly orthoacetate at last, 132g must be measured in bp.145～148 ℃, gas chromatographic analysis content is greater than 98%, reaction yield 80%.
Claims (6)
1, a kind of method for preparing alkyl ortho-acetate, it is characterized in that according to acetonitrile, anhydrous fatty alcohol, Acetyl Chloride 98Min. mol ratio be the ratio of 1.0:1.5～3.5:0.8～1.3,-10～0 ℃ of dripping acetyl chloride in the mixture of acetonitrile, anhydrous fatty alcohol, after dripping end,-20～45 ℃ of salt-forming reactions 4～48 hours, in reaction solution, add anhydrous fatty alcohol then again, add-on is 2.0～5.0 times of acetonitrile mole number,-20～65 ℃ of alcoholysis reactions 4～24 hours, obtain alkyl ortho-acetate.
2, the method for preparing alkyl ortho-acetate according to claim 1, the mol ratio that it is characterized in that described acetonitrile, anhydrous fatty alcohol, Acetyl Chloride 98Min. is 1.0:2.1:1.0.
3, the method for preparing alkyl ortho-acetate according to claim 1 is characterized in that described salt-forming reaction is-5～25 ℃ of reactions 6 hours.
4, the method for preparing alkyl ortho-acetate according to claim 1 is characterized in that described alcoholysis reaction is 25～45 ℃ of reactions 8 hours.
5, the method for preparing alkyl ortho-acetate according to claim 1 is characterized in that add-on at alcoholysis reaction stage Fatty Alcohol(C12-C14 and C12-C18) is 2.0 times of acetonitrile mole number.
6, the method for preparing alkyl ortho-acetate according to claim 1 is characterized in that described Fatty Alcohol(C12-C14 and C12-C18) is methyl alcohol or ethanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007101133388A CN100503540C (en) | 2007-10-10 | 2007-10-10 | Method for preparing alkyl orthoacetate |
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| CNB2007101133388A CN100503540C (en) | 2007-10-10 | 2007-10-10 | Method for preparing alkyl orthoacetate |
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| CN100503540C true CN100503540C (en) | 2009-06-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101844971B (en) * | 2010-05-06 | 2013-06-05 | 淄博职业学院 | Method for preparing alkyl ortho-acetate |
| CN102060678B (en) * | 2010-12-27 | 2014-02-19 | 江苏优士化学有限公司 | Synthesis process of trimethyl orthoacetate |
| CN103616464B (en) * | 2013-08-28 | 2015-05-20 | 南通天泽化工有限公司 | Quantitative analysis method for trimethyl orthoacetate |
| CN104072346A (en) * | 2014-06-19 | 2014-10-01 | 常州吉恩化工有限公司 | Method for preparing orthoester compound |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2645477C2 (en) * | 1976-10-08 | 1982-03-04 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of orthoacetic acid alkyl esters |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2645477C2 (en) * | 1976-10-08 | 1982-03-04 | Dynamit Nobel Ag, 5210 Troisdorf | Process for the preparation of orthoacetic acid alkyl esters |
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